EP3006491B1 - Raucharmer, flexibler isolationsschaum - Google Patents

Raucharmer, flexibler isolationsschaum Download PDF

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Publication number
EP3006491B1
EP3006491B1 EP14188135.9A EP14188135A EP3006491B1 EP 3006491 B1 EP3006491 B1 EP 3006491B1 EP 14188135 A EP14188135 A EP 14188135A EP 3006491 B1 EP3006491 B1 EP 3006491B1
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EP
European Patent Office
Prior art keywords
phr
chlorinated
material according
especially preferred
plasticizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP14188135.9A
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English (en)
French (fr)
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EP3006491A1 (de
Inventor
Christoph Zauner
Miroslav Bettermann
Heribert Quante
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Armacell Enterprise GmbH and Co KG
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Armacell Enterprise GmbH and Co KG
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Application filed by Armacell Enterprise GmbH and Co KG filed Critical Armacell Enterprise GmbH and Co KG
Priority to SI201430141A priority Critical patent/SI3006491T1/sl
Priority to ES14188135.9T priority patent/ES2617072T3/es
Priority to PT141881359T priority patent/PT3006491T/pt
Priority to DK14188135.9T priority patent/DK3006491T3/en
Priority to EP14188135.9A priority patent/EP3006491B1/de
Priority to HUE14188135A priority patent/HUE031875T2/en
Priority to LTEP14188135.9T priority patent/LT3006491T/lt
Priority to PL14188135T priority patent/PL3006491T3/pl
Priority to CA2900810A priority patent/CA2900810A1/en
Priority to AU2015215919A priority patent/AU2015215919A1/en
Priority to JP2015181032A priority patent/JP2016074883A/ja
Priority to KR1020150141175A priority patent/KR20160041817A/ko
Priority to US14/878,410 priority patent/US20160137801A1/en
Priority to CN201510646631.5A priority patent/CN105504573A/zh
Publication of EP3006491A1 publication Critical patent/EP3006491A1/de
Priority to HK16110009.0A priority patent/HK1221972A1/zh
Publication of EP3006491B1 publication Critical patent/EP3006491B1/de
Application granted granted Critical
Priority to HRP20170371TT priority patent/HRP20170371T1/hr
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/052—Closed cells, i.e. more than 50% of the pores are closed
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/06—Flexible foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2311/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2411/00—Characterised by the use of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a material for thermal and / or acoustic insulation comprising an expanded polymer (blend) based on PVC (polyvinyl chloride) and/or its copolymer(s) and/or its terpolymer(s) and at least one additional chlorinated organic polymer, the process of manufacturing such a material, and the use of such a material.
  • PVC polyvinyl chloride
  • FEF's Flexible elastomeric foams
  • Such materials are more or less solely based upon two different rubbers: nitrile butadiene rubber (NBR, often blended with PVC) or ethylene propylene diene rubber (EPDM).
  • NBR and NBR/PVC based FEF's are the most widespread polymers for standard FEF's, while EPDM is mainly used for applications requiring higher temperature resistance, e.g. solar applications.
  • EPDM based FEF's e.g.
  • EP2345535 claims a covering system comprising one layer of metal foil and one layer of glass fibre or two layers of glass fibres to cover common FEF's to achieve the best classification possible for organic based products (DIN EN 13501-1: B-s1, d0). Another approach is the use of an intumescent foil and a fabric layer on top of an FEF, but such system only achieves a "B-s2, d0" classification for sheets (Kaiflex ® KKplus s2 sheets). Furthermore, the FEF below such covering already needs to show a high level of flame resistance.
  • such coverings show in general several drawbacks: they are difficult to cut and less flexible compared to uncovered FEF foams, leading to difficulties and delays during installation. Furthermore, it is even more difficult to close the seams sufficiently to prevent them from opening in case of fire. Otherwise, the covering cannot securely prevent the FEF for a sufficient period of time from emitting huge quantities of smoke.
  • US 4082876 A discloses an expanded polymeric material as well as a method for chemically embossing a foamed composition without whitening and cracking of the surface by adding sulphur and synthetic rubber to a vinyl chloride resin preparation, wherein e.g. an acrylonitrile butadiene rubber (NBR) is used.
  • NBR acrylonitrile butadiene rubber
  • US 4692475 discloses a foamable polymeric composition
  • a foamable polymeric composition comprising at least one foamable polymer and/or monomer or coreactant and an effective amount of a blowing agent composition, wherein e.g. an acrylonitrile butadiene rubber (NBR) and polyvinyl chloride (PVC) are used in a weight ratio of 50 phr : 50 phr.
  • NBR acrylonitrile butadiene rubber
  • PVC polyvinyl chloride
  • EP2261305 claims an expanded elastomeric material comprising at least 50wt% (50 percent by weight) of polychloroprene (CR) based on the total polymer content. Such material achieves a "B-s2, d0" classification for sheets and a "B L -s1, d0" classification for tubes without additional covering (Armaflex ® Ultima).
  • CR polychloroprene
  • a major object of the present invention is to provide a FEF not showing the aforementioned disadvantages, means combining a low thermal conductivity ( ⁇ 0,037 W/m*K @ 0°C) with a high flame resistance and low smoke development for tubes and/or sheets (B L -s2, d0 / B-s2, d0 according to EN ISO 13823) at costs and densities comparable to the aforementioned NBR based FEF's without using brominated flame retardants.
  • the present invention provides an expanded polymeric material as disclosed in claim 1. Preferred embodiments are disclosed in claims 2 to 13.
  • such a versatile FEF material can be obtained by expanding and crosslinking a polymer blend of - on the one hand - at least 55 phr, preferably at least 65 phr of polyvinyl chloride (PVC) and/or vinyl chloride (PVC) copolymer and/or vinyl chloride (PVC) terpolymer and - on the other hand - at least 15 phr, preferably at least 25 phr of at least one additional chlorinated organic polymer that is crosslinkable by sulphur and/or metal oxides and/or thiadiazoles.
  • PVC polyvinyl chloride
  • PVC vinyl chloride
  • PVC vinyl chloride
  • PVC copolymer or PVC terpolymer can improve the flexibility and therefore workability of the material, especially when using PVC/EVA terpolymer. Due to the higher amount of chlorine within PVC compared to CPE (chlorinated polyethylene), less or even no additional flame retardant (especially brominated or boron based) is necessary to achieve the required levels of flame retardancy and low smoke development.
  • CPE chlorinated polyethylene
  • Phr (parts per hundred rubber) in the context of the current invention describes the total amount of all polymers, not limited to rubbers.
  • the vinyl chloride copolymer and/or vinyl chloride terpolymer comprises acetate or acrylate groups.
  • the vinyl chloride terpolymer is a vinyl chloride ethylene vinylacetate terpolymer (PVC/EVA terpolymer).
  • the additional chlorinated polymer is preferably polychloroprene (CR) and/or chlorosulfonated polyethylene (CSM) and/or chlorobutyl rubber (CIIR), preferably polychloroprene (CR) due to the highest level of chlorine and best balance between cost, processability and technical properties.
  • CR polychloroprene
  • CSM chlorosulfonated polyethylene
  • CIIR chlorobutyl rubber
  • the claimed material further comprises at least one filler, and may additionally comprise at least one plasticizer, at least one crosslinking system and at least one chemical blowing agent. Furthermore, the material may comprise additional flame retardants and additives to fulfil special demands and regulations defined by the area of application.
  • All quantities concerning the claimed material are related to a total of 100 phr of polymer content.
  • the total amount always comprises the aforementioned 100 phr of the polymer, too.
  • the overall quantities of all ingredients sum up to at least 300 phr, preferably at least 400 phr, but less than 1000 phr, preferably less than 850 phr, especially preferred less than 700 phr.
  • the polymer content related to the overall quantity of all ingredients is ⁇ 33,3 wt% (percent by weight), preferably ⁇ 25,0 wt%, but > 10,0 wt%, preferably > 11,8 wt%, especially preferred > 14,3 wt% (the given percentages are rounded to the first decimal place).
  • Higher polymer contents lead to worse fire performance, while lower polymer contents lead to a material of higher density as well as worse mechanical and insulation properties.
  • the polymer content may comprise at least 3 phr, preferably at least 5 phr of polybutadiene (butadiene rubber, BR) to improve processability and curing rate.
  • BR polybutadiene
  • the use of BR will improve the gas tightness in the early stage of vulcanisation and especially expansion due to its high curing rate. It furthermore helps using high amounts of PVC and/or its copolymer(s) and/or terpolymer(s) during a continuous vulcanisation and expansion process without counter-pressure. For the same reason, the use of BR can lower the density of the claimed material.
  • the polymer content of the claimed material may comprise all kind of polymers like - but not restricted to - ACM/AEM, AU/EU, BR, BIIR, CIIR, (G)(E)CO, EPM/EPDM, EVM, SBR, (H)NBR, FKM/F(E)PM, GPO, IR, IIR, (V)MQ, NR, T, PE, PP, PET, PBT, PC, PS, PA, PU, PTFE, PMMA etc.
  • non-halogenated polymers should be limited to less than 30 phr, preferably less than 20 phr, especially preferred to less than 10 phr.
  • the feasible quantity of non-halogenated polymers depends on the required fire and smoke performance as well as on the required dimensions and densities of the material, due to the impact on fire load.
  • the claimed material further comprises at least 80 phr, preferably at least 120 phr, especially preferred at least 160 phr of inorganic filler, preferably of metal and/or half metal chalcogen (i.e. compound of oxygen, sulphur) nature.
  • the inorganic filler may be an aluminium compound, such as aluminium silicates, oxides, hydroxides etc., e.g. ATH (aluminium hydroxide), and/or a silicon based compound, such as silicates, quartz, zeolites etc., or mineral based accordingly, e.g.
  • gypsum clay, huntite, hydromagnesite, perlite, vermiculite, chalk, slate, graphite, talc/mica etc., or any mixtures thereof.
  • inorganic fillers that cool down the fire by releasing water at temperatures above 180°C, or dilute or inhibit the oxygen supply of the flame by the release of carbon dioxide, carbon monoxide, etc. at temperatures above 180°C.
  • aluminium hydroxide (ATH), magnesium hydroxide, huntite and hydromagnesite due to the high level of water release. Furthermore, such materials do not increase the smoke development.
  • the claimed material may comprise at least 15 phr, preferably at least 30 phr, especially preferred at least 50 phr - related to the polymer content - of at least one plasticizer.
  • the plasticizers should have a positive impact on flame retardancy and smoke suppression.
  • preferred plasticizers are phosphate plasticizers or chlorinated plasticizers or mixtures thereof.
  • the chlorinated plasticizers are preferably chlorinated paraffins and/or chlorinated fatty acid substituted glycerines and/or chlorinated alpha-olefins having a chlorine content of at least 20 wt%, with respect to the weight of the chlorinated plasticizer, preferably at least 30wt%, especially preferred at least 45 wt% according to DIN 53474, especially preferred are long chain chlorinated plasticizers of C > 17.
  • Such highly chlorinated, long chain materials have the greatest fire retardant impact and are - in contrast to short or medium chain chlorinated plasticizers - not persistent, bio-accumulative or toxic.
  • plasticizers are still liquid at room temperature (19° - 23°C) and therefore significantly reduce the viscosity even at low processing temperatures ( ⁇ 80°C).
  • plasticizers have significantly less negative impact on smoke development in comparison to brominated flame retardants.
  • the phosphate plasticizers can be aliphatic, chloroaliphatic or aromatic phosphoric acid esters or any combinations thereof. Preferred are phosphoric acid esters of high phosphorous content and low smoke development; especially preferred is diphenyl 2-ethylhexyl phosphate (DPO) due to its marginal smoke emission, low viscosity and low temperature resistance.
  • DPO diphenyl 2-ethylhexyl phosphate
  • the claimed material may comprise at least one synergist for the halogen containing plasticizers / polymers and halogenated flame retardants (if present).
  • a synergist increases the effectivity of the flame retardants in the reaction to fire in terms of smoke suppression and/or heat release. Depending on the level of the desired fire retardancy, only combinations of a synergist and conventional fire retardants can achieve the desired results.
  • Preferred synergists are antimony (Sb), zinc (Zn), molybdeneum (Mo), tin (Sn), tungsten (W), bismuth (Bi), arsenic (As), vanadium (V) and/or zirconium (Zr) based materials, e.g.
  • antimony trioxide antimony pentoxide, zinc stannate, zinc hydroxystannate, zinc borate, zinc hydroxyborate, zinc molybdate, molybdenueum oxide, ammonium octamolybdate, stannous oxide, tungsten oxide, bismuth oxide, bismuth oxychloride, arsenic trioxide, arsenic pentoxide, vanadium oxide, zirconium oxide, etc, especially preferred are antimony trioxide and zinc borate.
  • the best balance of smoke suppression and flame retardancy can be achieved at quantities below 10 phr, preferably below 6 phr, especially preferred below 4 phr.
  • the claimed material furthermore may comprise at least one crosslinking system such as peroxides, triallylcyanurate, triallylisocyanurate, phenylmaleimide, thiadiazoles, fatty acid amide, hydrosilylation agents, radiation activators (for radiation or UV curing), sulphur systems, bisphenolics, metal oxides etc. Preferred are sulphur and/or metal oxide and/or thiadiazole based crosslinking systems.
  • the claimed material additionally may comprise at least one chemical blowing agent (e.g. releasing carbon dioxide, nitrogen or oxygen) chosen from the classes of organic blowing agents and/or inorganic blowing agents.
  • at least one chemical blowing agent e.g. releasing carbon dioxide, nitrogen or oxygen
  • organic blowing agents of nitroso type, azo type and/or aromatic hydrazide type especially preferred are azo type blowing agents like azodicarbonamide.
  • the claimed material may further comprise at least 10 phr, preferably at least 20 phr, especially preferred at least 30 phr flame retardants, preferably chlorinated flame retardants, especially preferred are long chain (C > 17) chlorinated paraffins being solid at room temperature (19° - 23°C) and having a chlorine content of at least 60% with respect to the weight of the chlorinated flame retardant (according to DIN 53474) and/or dechloranes (chlorinated cycloaliphatics) like Dechlorane A (Dechlorane Plus ® ), Dechlorane 602 and/or Dechlorane 603. While increasing the amount of chlorinated flame retardants within the material, the amount of synergists can be reduced, leading to a material of equal flame resistance at lower smoke emission.
  • chlorinated flame retardants especially preferred are long chain (C > 17) chlorinated paraffins being solid at room temperature (19° - 23°C) and having a chlorine content of at least 60% with respect to the weight
  • the claimed material furthermore may comprise a heat and/or reversion stabilizer system.
  • the stabilizers can be chosen from the classes of carbon blacks, metal oxides (e.g. iron oxide) and hydroxides (e.g. magnesium hydroxide), metal organic complexes, radical scavengers (e.g. tocopherol derivates), complex silicates (e.g. perlite, vermiculite), and combinations thereof.
  • the claimed material may further comprise ingredients like biocides, stabilizers (e.g. versus UV, ozone, reversion etc.), colours etc., of any kind in any ratio, including additives for improving its manufacturing, application and performance, such as inhibitors, retarders, accelerators, etc.
  • the claimed material may additionally comprise additives for char-forming and/or intumescent additives, like expanding graphite, for general protection purposes and/or to close and protect e.g. wall and bulkhead penetrations.
  • the claimed material may comprise substances that lead to a self-ceramifying effect in case of fire, like silicon containing compounds and/or internal adhesion promoters to ensure self-adhesive properties in co-extrusion and co-lamination applications, such as silicate esters, functional silanes, polyols, etc.
  • the claimed material can be mixed by standard methods widespread in the rubber industry, e.g. in a (Banbury ® ) mixer, single- or twin-screw extruder or on a mill. No specialized equipment is necessary to achieve sufficient dispersion.
  • the shaping of the claimed material can be carried out in extruders, presses, calanders, etc. Preferred are extruders due to the possibilities of easily forming sheets and tubes and vulcanize and expand them continuously within a hot air oven, microwave oven, salt bath, etc. Preferred are hot air and microwave ovens, because - among other things - no additional cleaning steps are necessary.
  • the claimed material can be expanded and crosslinked to a density of less than 80 kg/m 3 , preferably less than 60 kg/m 3 , especially preferred less than 50 kg/m 3 according to DIN EN ISO 845. Densities below 70 kg/m 3 and in particular below 50 kg/m 3 are preferred as they lead to a lower thermal conductivity.
  • the claimed material provides high water vapor transmission (WVT) values of ⁇ 7.000 or even ⁇ 10.000 according to EN13469 / EN 12086. For this reason, the application at low temperatures ( ⁇ 0°C) is feasible, because the object to be insulated is well protected from under insulation corrosion (UIC) through condensation of humidity.
  • WVT values are, inter alia, caused by a high share of closed cells, determined by vacuum water absorption of ⁇ 10,0%, preferably ⁇ 5,0%, especially preferred ⁇ 2,5% according to ASTM D 1056.
  • a major advantage of the claimed material is the suitability for applications where low flame spread and low smoke generation are required.
  • the claimed material can achieve a reliable B-s2, d0 / B L -s2, d0 classification according to DIN EN 13501-1 / EN ISO 13823 (SBI test) and achieves at least a reliable 25/50 classification according to CAN ULC S 102 / ASTM E84.
  • Another advantage of the claimed material is the possibility of using high amounts of PVC and /or its copolymer(s) and or terpolymer(s), which are available in large amounts at low costs and improve the flame retardancy and smoke suppression, although PVC is usually known as a material creating high amounts of black smoke.
  • the high level of non-crosslinked PVC and /or its copolymer(s) and or terpolymer(s) prevents the material from forming blisters and cracks due to improper ratio between expansion and vulcanisation.
  • the claimed levels of aforementioned non-crosslinked polymers and crosslinked polymers tolerate more or less a separation of vulcanisation and expansion even in manufacturing processes without counter-pressure. This means, that the claimed material can be vulcanized in a first step and afterwards expanded in a second step.
  • Another advantage of the claimed material is the broad range of (compressive) strength and flexibility the claimed material can be adjusted to, depending - on the one hand - on the level and ratio between plasticizers and PVC (including its homopolymers and terpolymers) and - on the other hand - the ratio between PVC and its homopolymers and/or terpolymers.
  • a high strength and stiffness can be achieved when using high levels of PVC and low levels of PVC copolymers, PVC terpolymers and plasticizers.
  • Such a material is favourable for applications like multilayer systems, buried insulations or insulations encased in concrete, screed, or the like.
  • a high flexibility can be achieved when using higher levels of PVC terpolymer(s) and/or PVC copolymer(s) and/or plasticizers and low levels of PVC. Such materials are preferred for applications requiring high flexibility, like insulation in private and public buildings, where the majority of insulation is drawn or applied to pipes, elbows, ducts, etc.
  • a major advantage of the claimed material is the excellent suitability of the material for thermal and acoustic insulation.
  • the material achieves a thermal conductivity of ⁇ 0,037 W/m*K at 0°C (according to DIN EN 12667 / DIN EN ISO 8497) and densities below 63 kg/m 3 (according to DIN EN ISO 845).
  • a major advantage in comparison to NBR/PVC based FEF's is the improved weathering and ozone resistance, enabling the use of the claimed material for outdoor applications without additional protective covering.
  • the claimed material is its versatility regarding the production equipment. It can be produced in an economic way in a continuous process, e.g. by extrusion, co-lamination or direct co-extrusion.
  • the material can also be laminated, moulded, co-moulded, overmoulded, welded etc. directly as mono- or multilayer system and thus it can be applied in unrestricted shaping onto various surfaces in automotive, transport, aeronautics, building and construction, marine and offshore, furniture, machinery engineering and many other industries, even by thermoforming or other shaping methods.
  • the claimed material can particularly be manufactured in the form of tubes and sheets in a continuous process in various wall thicknesses and inner diameters; most suitable are wall thicknesses between 3 and 100mm.
  • Wall thicknesses above 100mm tend to have some drawbacks regarding their technical properties. Most of the currently available FEF's are only available in thicknesses up to 50mm or show significant drawbacks regarding their fire classification (e.g. Kaiflex ® 60/80/100, fire classification according to DIN EN 13501-1: E).
  • a further advantage of the claimed material is the high resistance against acids, oils, lubricates and sea water.
  • Another advantage of the claimed material is that no questionable plasticizers are needed, like phthalate plasticizers, short or medium chain chlorinated paraffins (C ⁇ 18) which are suspected of being e.g. persistent, bio-accumulative, toxic etc.
  • the compounds were mixed in an internal batch mixer (Banbury ® mixer) with an average mixing time of 10 minutes and an average dumping temperature of 140°C.
  • the compounds were homogenized further on a roller mill and the blowing agent and crosslinking system were added to the roller mill after cooling down the compound to less than 90°C.
  • the extrusion was performed on a strip feeded single screw vacuum extruder providing unexpanded and unvulcanized sheets and tubes. Those were crosslinked and expanded afterwards in a hot air oven cascade of 5 ovens to sheets of 25 mm wall thickness and tubes of 25 mm wall thickness and 22 mm inner diameter.
  • Table 1 lists the raw materials used for the compounds.
  • Table 2 gives an overview of all materials tested.
  • Table 3 shows the recipes of the innovative examples (compounds) without additives and crosslinking agents (referred to as "additives").
  • Table 1 Raw materials Chemical Name Trade Name Supplier Polyvinyl chloride (PVC) Vinnolit ® S3265 Vinnolit, Germany vinyl chloride ethylene vinylacetate terpolymer (PVC/EVA terpolymer) Vinyl Resin LC13-1 Shexian Sinfeng Chem.Co.Ltd, China vinyl chloride vinyl acetate copolymer (PVC/VA copolymer) KanevinylTM MB1008 Kaneka Corporation, Japan Polychloroprene (CR) Neoprene ® WM-1 DuPont ® , USA Chlorosulfonated Polyethylene (CSM) TOSO-CSM ® TS-430 Tosoh Corporation, Japan Chlorobutyl rubber (CIIR) ExxonTM Chlorobutyl 1066 ExxonMobil Corporation, USA Butadiene rubber (BR) Buna ® CB 24 F Lanxess, Germany Chloroparaffin (CP) Cereclor ® 46 Ineos ®
  • Table 2 shows an overview of the tested materials and their basic compositions. All materials were available as sheets in 25mm wall thickness and tubes in 25mm wall thickness and 22mm inner diameter. Materials marked with an "*" are comparative examples, the other materials are innovative examples. Table 2: Comparative and innovative examples No.
  • Table 4 presents the flammability test results of all innovative and comparative examples.
  • the SBI test was performed on both tubes and sheets (except from comparative example 4, which is only available as sheet material), the ASTM E84 test was performed on sheets only.
  • Table 5 presents the densities (according to DIN EN ISO 845), thermal conductivities (according to DIN EN 12667) and water vapour transmission values (WVT, according to EN 12086) test results of all examples (limited to sheets).
  • Table 4 Flammability test results of all examples Material SBI (EN 13823) ASTM E 84 sheets tubes sheets 1* E E 65/380 2* B-s3, d0 B L -s3, d0 20/320 3* B-s3, d0 B L -s2, d0 15/380 4* B-s2, d0 --- 20/80 5* B-s2, d0 B L -s1, d0 5/30 6* C-s3, d0 B L -s3, d0 25/190 7 B-s3, d0 B L -s2, d0 18/60 8 B-s2, d0 B L -s2, d0 20/50 9 C-s2, d0 B L -s2, d0 23/40 10 B-s2, d0 B L -s1, d0 15/30 11 B-s2, d0 B L -s2, d0 20/25
  • Table 5 Density, thermal conductivity and WVT of all examples Material Density Thermal conduct

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Claims (15)

  1. Geschäumtes Polymermaterial, erhalten aus einem schäumbaren Polymermaterial, das aus wenigstens 300 phr, vorzugsweise wenigstens 400 phr, jedoch weniger als 1000 phr, vorzugsweise weniger als 850 phr und besonders bevorzugt weniger als 700 phr Komponenten insgesamt besteht, umfassend eine Gesamtheit von 100 phr aus wenigstens zwei Polymeren, von denen
    1) wenigstens 55 phr, vorzugsweise wenigstens 65 phr auf Polyvinylchlorid (PVC) oder Vinylchlorid-Copolymer oder Vinylchlorid-Terpolymer oder ein Gemisch davon entfallen und
    2) wenigstens 15 phr, vorzugsweise wenigstens 25 phr auf wenigstens ein zusätzliches chloriertes organisches Polymer entfallen und wenigstens 80 phr, vorzugsweise wenigstens 120 phr, besonders bevorzugt wenigstens 160 phr auf wenigstens einen anorganischen Füller entfallen, wobei das wenigstens eine zusätzliche chlorierte organische Polymer mit Schwefel und/oder Metalloxiden oder Thiadiazolen vernetzt ist.
  2. Material nach Anspruch 1, wobei das Vinylchlorid-Copolymer und/oder Vinylchlorid-Terpolymer Acetat- oder Acrylatgruppen umfassen.
  3. Material nach Anspruch 1 oder 2, wobei das Vinylchlorid-Terpolymer ein Vinylchlorid-Ethylenvinylacetat-Terpolymer (PVC/EVA-Terpolymer) ist.
  4. Material nach Anspruch 1, wobei das zusätzliche chlorierte organische Polymer Polychloropren (CR) und/oder chlorsulfoniertes Polyethylen (CSM) und/oder Chlorbutylkautschuk (CIIR), vorzugsweise Polychloropren (CR) ist.
  5. Material nach einem der Ansprüche 1 - 4, umfassend wenigstens 3 phr, vorzugsweise wenigstens 5 phr Polybutadien.
  6. Material nach einem der Ansprüche 1 - 5, umfassend wenigstens einen Weichmacher, der in der Formulierung mit wenigstens 15 phr, vorzugsweise mit wenigstens 30 phr, besonders bevorzugt mit wenigstens 50 phr vorliegt.
  7. Material nach Anspruch 6, wobei wenigstens 1 Weichmacher ein chlorierter Weichmacher wie chloriertes Paraffin und/oder chloriertes fettsäuresubstituiertes Glycerin und/oder chloriertes α-Olefin, vorzugsweise ein chlorierter Weichmacher mit einem Chloringehalt von wenigstens 20 Gew.-%, vorzugsweise von wenigstens 30 Gew.-%, besonders bevorzugt von wenigstens 45 Gew.-% ist, bezogen auf das Gewicht des chlorierten Weichmachers, nach DIN 53474, besonders bevorzugt ein langkettiger chlorierter Weichmacher mit einer Mindestkettenlänge von C > 17.
  8. Material nach Anspruch 6, wobei wenigstens 1 Weichmacher ein Phosphatweichmacher, vorzugsweise ein Phosphorsäureester, besonders bevorzugt ein Diphenyl-2-ethylhexylphosphat (DPO) ist.
  9. Material nach einem der Ansprüche 1 - 8, umfassend wenigstens 10 phr, vorzugsweise wenigstens 20 phr, besonders bevorzugt wenigstens 30 phr wenigstens eines chlorierten Flammschutzmittels, vorzugsweise ein bei Raumtemperatur, d.h. zwischen 19 und 23 °C, festes langkettiges chloriertes Paraffin mit wenigstens einem Chlorgehalt von wenigstens 60 %, bezogen auf das Gewicht des chlorierten Falmmschutzmittels nach DIN 53474.
  10. Material nach einem der Ansprüche 1 - 9, wobei der anorganische Füller auf einem Metall und/oder einem Halbmetallchalcogen beruht, vorzugsweise anorganische Füller darstellt, die Wasser und/oder CO2 und/oder CO bei Temperaturen von über 180 °C freisetzen, besonders bevorzugt Aluminiumhydroxid, Magnesiumhydroxid, Huntit und/oder Hydromagnesit.
  11. Material nach einem der Ansprüche 1 - 10, umfassend wenigstens einen Synergisten für die chlorierten Flammschutzmittel und/oder chlorierten Weichmacher und/oder chlorierten Polymere, vorzugsweise Antimonytrioxid oder Zinkborat oder ein Gemisch davon.
  12. Material nach einem der Ansprüche 1 - 11, das bis zu einer Dichte von unter 80 kg/m3, vorzugsweise von unter 60 kg/m3, besonders bevorzugt von unter 50 kg/m3 nach DIN EN ISO 845 geschäumt ist.
  13. Material nach einem der Ansprüche 1 - 12, das eine geschlossenzellige Struktur aufweist, ermittelt durch Vakuumwasserabsorption von < 10,0 %, vorzugsweise von < 5,0 %, besonders bevorzugt von < 2,5 % nach ASTM D 1056.
  14. Verfahren zur Herstellung des Materials nach einem der Ansprüche 1 - 13, wobei das Polymermaterial durch Zersetzung eines chemischen Blähmittels, vorzugsweise vom Nitrosotyp, Azotyp und/oder aromatischem Hydrazidtyp, besonders bevorzugt Azodicarbonamid, geschäumt wird.
  15. Verwendung eines Materials nach einem der Ansprüche 1 - 13 zur Wärme- und/oder Schallisolierung.
EP14188135.9A 2014-10-08 2014-10-08 Raucharmer, flexibler isolationsschaum Revoked EP3006491B1 (de)

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SI201430141A SI3006491T1 (sl) 2014-10-08 2014-10-08 Malodimna gibka izolacijska pena
ES14188135.9T ES2617072T3 (es) 2014-10-08 2014-10-08 Espuma de aislamiento flexible con baja emisión de humos
PT141881359T PT3006491T (pt) 2014-10-08 2014-10-08 Espuma de isolamento flexível e de fumo reduzido
DK14188135.9T DK3006491T3 (en) 2014-10-08 2014-10-08 Flexible insulation foam with low smoke generation
EP14188135.9A EP3006491B1 (de) 2014-10-08 2014-10-08 Raucharmer, flexibler isolationsschaum
HUE14188135A HUE031875T2 (en) 2014-10-08 2014-10-08 Low-smoke, flexible insulation
LTEP14188135.9T LT3006491T (lt) 2014-10-08 2014-10-08 Išskiriančios mažai dūmų, lanksčios izoliacinės putos
PL14188135T PL3006491T3 (pl) 2014-10-08 2014-10-08 Elastyczna pianka izolacyjna o niskiej emisji dymu
CA2900810A CA2900810A1 (en) 2014-10-08 2015-08-18 Low smoke, flexible insulation foam
AU2015215919A AU2015215919A1 (en) 2014-10-08 2015-08-20 Low Smoke, Flexible Insulation Foam
JP2015181032A JP2016074883A (ja) 2014-10-08 2015-09-14 低煙、軟質断熱防音発泡体
KR1020150141175A KR20160041817A (ko) 2014-10-08 2015-10-07 저연, 가요성 절연 폼
US14/878,410 US20160137801A1 (en) 2014-10-08 2015-10-08 Low smoke, flexible insulation foam
CN201510646631.5A CN105504573A (zh) 2014-10-08 2015-10-08 低烟雾、柔性隔绝泡沫
HK16110009.0A HK1221972A1 (zh) 2014-10-08 2016-08-23 低煙霧、柔性隔絕泡沫
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CN111434710B (zh) * 2019-01-14 2022-11-11 阿乐斯企业有限及两合公司 高耐火性发泡聚合物材料
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ES2617072T3 (es) 2017-06-15
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CN105504573A (zh) 2016-04-20
HRP20170371T1 (hr) 2017-05-05
AU2015215919A1 (en) 2016-04-28
EP3006491A1 (de) 2016-04-13
SI3006491T1 (sl) 2017-03-31
CA2900810A1 (en) 2016-04-08
HUE031875T2 (en) 2017-08-28
DK3006491T3 (en) 2017-02-27
KR20160041817A (ko) 2016-04-18
HK1221972A1 (zh) 2017-06-16
JP2016074883A (ja) 2016-05-12
LT3006491T (lt) 2017-02-27
US20160137801A1 (en) 2016-05-19

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